Cotton-tung oil durable-press textiles with high flex abrasion resistance

ABSTRACT

Cotton fabric is impregnated with one of several organic solutions containing tung oil and subjected to either a highenergy radiation treatment or to a specific heat treatment, thus initiating a reaction with the cellulose which yields a cotton fabric with durable-press properties. Of special interest is the unusually high flex abrasion resistance obtained.

United States Patent 1 1 Harris et al.

[ Dec. 16, 1975 COTTON-TUNG OIL DURABLE-PRESS TEXTILES WITH HIGH FLEX ABRASION RESISTANCE Inventors: James A. Harris, Pearl River; Jett C.

Arthur, Jr., Metairie, both of La.

The United States of America as represented by the Secretary of Agriculture, Washington, DC.

Filed: Nov. 26, 1974 Appl. No.: 527,399

Assignee:

US. Cl 8/116 R; 8/115.6; 8/193; 8/194; 106/252; 204/l59.12; 260/23 CP; 260/23 ST; 427/36; 427/352; 427/382; 427/392 Int. C1. D06M 13/02; D06M 13/20 Field of Search 427/308, 392, 36; 106/252; 8/115.6,116 R, 193, 194

References Cited UNITED STATES PATENTS 1/1929 Cochran 8/ll5.6

1,984,139 12/1934 Koch 106/252 2,381,653 8/1945 Drummond 2,890,137 6/1959 Vaughan et al 427/392 3,101,276 8/1963 Hendricks 427/308 3,488,210 1/1970 Kuzmak et al......... 8/116 R 3,514,385 5/1970 Magat et a1 8/193 Primary ExaminerMurray Tillman Assistant Examiner-Arthur l-I. Koeckert Attorney, Agent, or FirmM. Howard Silverstein; Max D. Hensley [5 7 ABSTRACT 13 Claims, No Drawings COTTON-TUNG OIL DURABLE-PRESS TEXTILES WITH HIGHFLEX ABRASION RESISTANCE This inventionrelatesto-a process for chemically treating cotton fabrics. More specifically, this invention 7 relates to the impregnation of cotton fabric with a naturally occurring productto improve its physical properties. Cotton fabric isimpregnated with tung oil, which is obtained from the fruit of the tree Aleuri tes fora'ii, and then subjected to a high energy radiation. treatment and/or a heat treatment to yield a cotton textile with durablepress properties, such as improved wrinkle recovery after deformation and improved flex abrasion resistance, thereby increasing the utility of cotton textile products in markets requiring easy care properties.

The actual processing canbe described in a-plural manner to yield at least three processes, thusly:

1. Solutions of tung oil in organic solvents, such as acetone, N,N-dimethylformamide, methyl ethyl ketone, and petroleum ether, are padded onto cotton textile fabrics. The physical properties of these treated cotton textile fabrics are permanently modified by thermally and/or high energy radiation initiated oxidative 2 occur. .We have discovered that a naturally occurring chemical, tung oil, can be padded onto cotton fabrics to yield all-cotton textiles with durable-press properties. Tung oil, obtained from the fruit of the tree Aleurites fordiz' grown in the southern area of the United States of America and other countries, is a glycerine derivative of stearic acid with about 75 percent ofthe acid composed of eleostearic acid, which contains three conjugated double bonds, while padded onto cotton textile fabrics can be oxidatively polymerized by thermal-and/or high energy radiation initiation. We found that this oxidative polymerization of the tung oil leads to changes in the morphological structures of the cotton textile fabrics and in the physical properties of the tung oil modified fabrics to impart durable-press properties to the cotton textile fabrics.

We have now discovered that when tung oil from solutions of organic solvents, such as acetone, N,N- dimethylformamide, methyl ethyl ketone, and petroleum ether, are padded onto cotton textile fabrics to i add-ons of tung oil ranging from 10 to 29 percent and polymerization of the added tung oil to yield textile products with durable-press properties.

2. Solutions of tung oil in organic solvents, such as acetone, N,N-dimethylformamide, methyl ethyl ketone, and petroleum ether, containing vinyl monomers, such as acrylonitrile, 1,3-butylene dimethacrylate, diacetone acrylamide, glycidyl methacrylate, or styrene, are padded onto cotton textile fabrics. The physical properties of the treated cotton textile fabrics are permanently modified by thermally and/or high energy radiation initiated polymerization of the added tung oil and vinyl monomer to yield textile products with durable-press properties.

3. Solutions of tung oil in organic solvents, such as acetone, N,N-dimethylformamide, methyl ethyl ketone, and petroleum ether, are padded onto cotton textile fabrics, then cellulosic crosslinking reagents are padded onto the tung oil treated cotton textile fabrics either before or after the oxidative polymerization of the tung oil has been thermally initiated, and finally thermally curing the tung oil treated cotton textile fabrics containing cellulosic crosslinking reagents to yield textile products with durable-press properties.

The process of this invention has as its objective the modification of the morphological structures of cotton textile fabrics by deposition of chemical reagents in solution within the morphological structures of the fabrics and then oxidatively polymerizing said chemical reagents within the morphological structures of the fabrics by thermal and/or high energy radiation initiation. Thereby a cotton textile fabric product is prepared which has durable-press properties, particularly retention and recovery of initial shape after deformation, that is wrinkle recovery and flex abrasion resistance, so that durable-press cotton textile products with easy care properties are obtained.

Developments in the commercial use of durablepress textiles have generally led to the use of blends of cotton fibers andman-made chemical fibers in order to have products with easy care properties with minimum losses of the natural properties of cotton. When all-cotton fabrics are finished by normally used processes in which selected reagents are curedwith chemical catalysts at high temperatures on the fabrics, usually drastic.

cured at temperatures ranging from 200 to 300 F at times ranging from 2 to 8 minutes and/or irradiated at ambient temperatures.( about 77F) by cobalt-6O gamma-radiation to dosages ranging from 1 to 2.3 megarads, durable-press cotton textile products with improved properties over those of durable-press cotton textile products prepared by the usual thermally and chemically catalyzed crosslinking processes. We have further discovered that if vinyl monomers, such as acrylonitrile, 1,3-butylene dimethylacrylate, diacetone acrylamide, glycidyl methacrylate, or styrene are added to the solutions of tung oil in ratios ranging from 1 part of tung oil and 1 part of vinyl monomer to 7 parts of tung oil and 1 part of vinyl monomer prior to the padding and subsequent processing steps, durable-press cotton textile products with improved properties over those of durable-press cotton textile products prepared by the usual thermally and chemically catalyzed crosslinking processes. Further, we have found that the usual crosslinking chemical reagents, without the addition of chemical catalysts, which are primarily responsible for the drastic losses in the desirable natural properties of cotton fabrics, may be combinedwith the tung oil treatment of cotton fabrics either prior to or after oxidative polymerization of the tung oil within the cotton fabric structure to yield durable-press cotton textile products with improved properties over those of cotton textile products prepared by the usual processes.

The following examples are provided to illustrate the invention and are not to be construed as limits to the invention in any manner whatsoever.

EXAMPLE 1 Heat Curing and Add-on Study Cotton fabric (printcloth about 3.4 oz/yd which had been enzymatically desized, alkali scoured, peroxide bleached, and dried to normal regain moisture content was immersed in about 30) percent solution of tung oil in N,N-dimethylformamide for 2 hours or more at 77F until the cotton fabric was thoroughly wetted with the solution; then the cotton fabric was padded to the desired wet pickup of about 80l20%. The tung oil treated cotton fabric was dried for 3 minutes at about F in an air oven.

The six samples of the dried, tung oil-treated cotton fabric were cured for different times at different temperatures (see Table 1, samples 4-9, and controls 1-3). Selected durable-press properties of these cured, tung oil treated fabrics were compared with those of untreated cotton fabric, heated untreated cotton fabric, and cotton fabric crosslinked with dimethyloldihydroxyethylene urea (DMDHEU) and cured with chemical catalysts at 320F for 6 minutes in accordance with prior art. DMDHEU add-on was 8%. The selected durable-press properties of the fabrics were determined in accordance with methods of the American Society for Testing and Materials, Philadelphia, Pa., as follows: l) tear strength, ASTM method D 1424-63; (2) flex abrasion resistance, ASTM method D 1175-64T; and (3) wrinkle recovery angle, ASTM D' l295-60T. The selected durable-press properties of the fabrics are tabulated below (see Table 1).

TABLE l 4 ded, and dried (using the method of Example 1). Then samples of the dried, tung oil treated cotton fabric were cured at 300 F for 6 minutes. Then these cured, tung oil treated fabrics were extracted with selected organic solvents'and dried. Then selected durable-press properties of the fabrics were determined and are tabulated below. The control fabrics were the same as those in Example I. The'tung oil'treated fabrics, which had been immersed in solutions of tung oil and N,N-dimethylformamide and, after curing, extracted with methyl ethyl ketone had wrinkle recovery angle of 260, tear strength of 493 grams, and flex abrasion resistance of 976 cycles which were improved selected durable-press properties, as compared with other tung oil treated fabrics and fabrics cross-linked by the method of prior art, as examination of data'in Examples 1 and 2 show Effects of Temperature and Time of Curing on the Properties of Tung Oil Cotton Fabrics Flex W rinkle Sample Temp. Time Tung Oil Tear Abrasion Recovery No. "F min. Add-On Strength Resistance, Angle-Wet,

7: grams cycles degress Control Fabrics l 820 7 l 3 l 95 Research Fabrics (a) Dimethyloldihydroxyethylene urea add-on 8 percent by method of prior art.

The tung oil treated cotton fabrics, which contained (see Table II).

TABLE II Effects of Solvent Used to Prepare Solution of Tung Oil on the Properties of Tung Oil Cotton Fabrics MEK. methyl ethyl ketone; DMF, N,N-dimethylformamide; PE, petroleum other; A, acetone; MEK-DMF. equal parts; DMF-PE. equal parts; DMF-A. cqual pans.

EXAMPLE 2 Evaluation of Solvents Cotton fabrics were prepared (using the method of Example 1) and immersed in solutions of tung oil, pad- EXAMPLE 3 I Tung Oil, Acrylonitrile, Heat and Radiation:

' Cotton fabrics were prepared (using the method of Example 1) and immersed in solutions of tung oil and acrylonitrile in N,N-dimethylformamide, padded, and dried (using the method of Example 1). Then samples of the dried, tung oil acrylonitrile treated cotton 1 fabric were cured at 300 F for 6 minutes. Then these cured samples were irradiated with gamma-radiation from cobalt-6O to desired dosages. Selected durablepress properties of the fabrics were determined and are tabulated below. The control fabrics were the same as those in Example 1. Y

TABLE n .t 1 a 5 Effects of Added Acrylonitrile and Radiation Dosageon the Properties of Tung Oil Cotton Fabrics Flex Wrinkle Sample Ratio in Parts Add-On, 'Ra' diation Tear Abrasion Recovery 1 i No. of Tung Oil 7: Dosage, Strength. Resistance, AngleWet.-

to Monomer I p megarad grams cycles degrees I 7:1 36 2 v 393 713 I 256 16 3:1 47 2.3 320 587 257 17 3:1 29 1.8 460 i 858 275 18 3:1 -2 3- 1.1 553 1180 267 19 1:1 I 33 2 320 496 251 Cotton fabric crosslinked by the method of the prior over those of fabric prepared by the method of the art (see control fabrics of Example 1) had wrinkle 15 prior art (see Table IV).

recovery angle-wet of 277, tear strength of 207 grams, We claim:

and flex abrasion resistances of 13 cycles, as compared 1. A process for imparting to cotton fabrics improved with fabrics prepared by method of Example 3 of durable-press properties, the process comprising: 25l275, 320-353 grams, and 496-1180 cycles. Oba. impregnating a cotton fabric with a 10-30% soluviously, the overall durable-press properties of fabrics 20 tion of tung oil in an organic solvent selected from prepared by the method of Example 3 were improved the group consisting of N,N-dimethylformamide, over those of fabric prepared by the method of the methyl ethyl ketone, a 50-50 mixture of N,N- prior art (see Table III). dimethylformamide and acetone, and a 50--50 mixture of N,N-dimethylfiormamide and petroleum EXAMPLE 4 ether, to a wet pickup of about from 80 to 120%, Evaluation of Monomers b. drying the impregnated fabric of (a) with heat applied at about 140F. for about 3 minutes, c. curing the dried fabric at about from 200 to 300F. for about from 2 to 8 minutes, d. washing the cured fabric in organic solvent se- Cotton fabrics were prepared (using the method of Example 1) and immersed in solutions of tung oil and vinyl monomer (IO-%) (acrylonitrile, styrene, diacetone acrylamide, glycidyl methacrylate, or 1,3-buty- 30 lene dimethacrylate) in N,N-dimethylformamide so lected l the group l of f volume-%) plus methyl ethyl ketone (20 volume-%), formamlde methyl ethyl ketone or a mlxmre padded to wet pickups of 5 0250% to yield add-ons of h and 15 to 68%, and dried (using the method of Example e. drying the cured and washed cotton-tung 011 fabric Then samples of the dried, tung oil vinyl monomer thus produced treated cotton fabric were cured at 300 F. for 6 min- The Process of Clam} 1 Wherem the Organic Solvent utes. Then these cured samples were irradiated with m NN'dlmethylformaimde' gamma radiation from c Oba1t 60 to a dosage of 1 mega 3. The Process of claim 1 wherein the organic solvent rad. Some of these samples were immersed in hydramethyl ethyl ketonei zine solution for 17 hours, as indicated in the tabulation 40 The proces? of clalm 1 whelem the orgamc.solvem below, to improve the odor of the fabrics. Selected IS a 50 mlxture of NN'dlmethylformamlde and durable-press properties of the fabrics were determined acetone and are tabulated below. The control fabrics were the The procesis of claim 1 whelein the organic Solvent Same as those in Example 1s a 5050 mlxture of N,N-d1methylformamide and TABLE IV Efi'ects of Monomer Addition and Thermal Plus Radiation Curing on the Properties of Tung Oil Cotton Fabrics Flex Wrinkle Sample Ratio in Parts Add-On, Tear Abrasion Recovery No. Monomer of Tung Oil Strength, Resistance, Angle-Wet,

to Monomer grams cycles degrees 20 AN" 2.5: 1 15 620 924 240 21 AN 2.521 36 460 1066 254 22 St 2.5: 1 32 573 1456 252 23 St 2.5: 1 39 420 1067 253 24 DAA 1.3: l 38 433 474 259 25 GMA 1.3: 1 68 327 390 246 26 BDMA 2: 1 48 100 95 259 AN acryloniirile; St styrene; DAA diacetone acrylamide; GMA glycidyl methacrylate; BDMA l,3-butylene dimethacrylate. Immersed in hydrazine solution.

Cotton fabrics crosslinked by the method of the prior petroleum ether.

art (see control fabrics of Example 1) had wrinkle 6. A process for imparting to cotton fabrics improved recovery angles-wet of 277 tear strength of 207 grams, durable-press properties, the process comprising:

and flex abrasion resistances of 13 cycles, as compared a. impregnating a cotton fabric with a 10-30% soluwith fabn'cs prepared by method of Example 4 of tion of a mixture of tung oil and a vinyl monomer 240259, 327-620 grams, and 390-1456 cycles. Obselected from the group consisting of acrylonitrile, viously, the overall durable-press properties of fabrics styrene, diacetone acrylamide, glycidyl methacryprepared by the method of Example 4 were improved late, and 1,3-butylene dimethacrylate, in a ratio in parts of tung oil to vinyl monomer about from 7:1 to 1:1, respectively; said mixture in an organic solvent selected from the group consisting of N,N- dimethylformamide and an 80-2O (by volume) mixture of N,N-dimethylformamide and methyl ethyl ketone, to obtain a wet pickup of about from 50 to 250% of yield add-ons of to'68%,

b. drying the impregnated fabric of (a) with heat applied at about 140F. for about 3 minutes,

c. curing the dried fabric at about 300F. for about 6 minutes,

d. irradiating the cured fabric with gamma-radiation from cobalt-6O to radiation dosages ranging from about 1 to 2.3 megarads at a temperature of about 77F to obtain a cotton-tung oil-vinyl polymerized fabric, I

e. washing .the irradiated fabric in N,N-dimethylformamide, and i f. drying the cured, irradiated, and washed cottontung oil-vinyl polymerized fabric.

7. The process of claim 6 wherein the vinyl monomer is acrylonitrile.

8. The process of claim 6 wherein the vinyl monomer is styrene.

9. The process of claim 6 wherein the vinyl monomer is diacetone acrylamide.

10. The process of claim 6 wherein the vinyl monomer is glycidyl methacrylate.

11. The process of claim 6 wherein the vinyl monomer is 1,3-butylene dimethacrylate.

12. The process of claim 6 wherein the organic solvent is N,N-dimethylformamide 13. The process of claim 6 wherein the organic solvent is an -20 mixture of N,N-dimethylformamide and methyl ethyl ketone. 

1. A PROCESS FOR IMPARTING TO COTTON FABRICS IMPROVED DURABLE-PRESS PROPERTIES, THE PROCESS COMPRISING: A. IMPREGNATING A COTTON FABRIC WITH A 10-30% SOLUTION OF TUNG OIL IN AN ORGANIC SOLVENT SELECTED FROM THE GROUP CONSISTING OF N,N-DIMETHYLFORMAMIDE, METHYL ETHYL KETONE, A 50-50 MIXTURE OF N,N-DIMETHYLFORMAMIDE AND ACETONE, AND A 50-50 MIXTURE OF N,N-DIMETHYLFORMAMIDE AND PETROLEUM ETHER, TO A WET PICKUP OF ABOUT FROM 80 TO 120%, B. DRYING THE IMPREGNATED FABRIC OF (A) WITH HEAT APPLIED AT ABOUT 140*F. FOR ABOUT 3 MINUTES, C. CURING THE DRIED FABRIC AT ABOUT FROM 200* TO 300*F. FOR ABOUT FROM 2 TO 8 MINUTES, D. WASHING THE CURED FABRIC IN ORGANIC SOLVENT SELECTED FROM THE GROUP CONSISTING OF N-N-DIMETHYLFORMAMIDE, METHYL ETHYL KETONE OR A MIXTURE THEREOF, AND E. DRYING THE CURED AND WASHED COTTON-TUNG OIL FABRIC THUS PRODUCED.
 2. The process of claim 1 wherein the organic solvent in N,N-dimethylformamide.
 3. The Process of claim 1 wherein the organic solvent is methyl ethyl ketone.
 4. The process of claim 1 wherein the organic solvent is a 50-50 mixture of N,N-dimethylformamide and acetone.
 5. The process of claim 1 wherein the organic solvent is a 50-50 mixture of N,N-dimethylformamide and petroleum ether.
 6. A process for imparting to cotton fabrics improved durable-press properties, the process comprising: a. impregnating a cotton fabric with a 10-30% solution of a mixture of tung oil and a vinyl monomer selected from the group consisting of acrylonitrile, styrene, diacetone acrylamide, glycidyl methacrylate, and 1,3-butylene dimethacrylate, in a ratio in parts of tung oil to vinyl monomer about from 7:1 to 1:1, respectively; said mixture in an organic solvent selected from the group consisting of N,N-dimethylformamide and an 80-20 (by volume) mixture of N,N-dimethylformamide and methyl ethyl ketone, to obtain a wet pickup of about from 50 to 250% of yield add-ons of 15 to 68%, b. drying the impregnated fabric of (a) with heat applied at about 140*F. for about 3 minutes, c. curing the dried faBric at about 300*F. for about 6 minutes, d. irradiating the cured fabric with gamma-radiation from cobalt-60 to radiation dosages ranging from about 1 to 2.3 megarads at a temperature of about 77*F to obtain a cotton-tung oil-vinyl polymerized fabric, e. washing the irradiated fabric in N,N-dimethylformamide, and f. drying the cured, irradiated, and washed cotton-tung oil-vinyl polymerized fabric.
 7. The process of claim 6 wherein the vinyl monomer is acrylonitrile.
 8. The process of claim 6 wherein the vinyl monomer is styrene.
 9. The process of claim 6 wherein the vinyl monomer is diacetone acrylamide.
 10. The process of claim 6 wherein the vinyl monomer is glycidyl methacrylate.
 11. The process of claim 6 wherein the vinyl monomer is 1,3-butylene dimethacrylate.
 12. The process of claim 6 wherein the organic solvent is N,N-dimethylformamide.
 13. The process of claim 6 wherein the organic solvent is an 80-20 mixture of N,N-dimethylformamide and methyl ethyl ketone. 